Perfume and flavored compositions containing ethyl 2,4-dioxohexanoate

ABSTRACT

The present invention comprises perfume and flavored compositions containing ethyl 2,4-dioxohexanoate.

United States Patent Hajos et al. Jan. 14, 1975 PERFUME AND FLAVORED [58] Field of Search 426/65, [75

COMPOSITIONS CONTAINING ETIIYL 2,4-DIOXOIIEXANOATE [56] References Cited [75] Inventors: Zoltan G. Hajos, Upper Montclair; OTHER PUBLICATIONS f Parmh" Glen Rldge both Fenarolis Handbook of Flavor Ingredients, Edited by O Furia et al., 1971, The Chemical Rubber Co., Cleve- [73] Assignee: Hoffmann-La Roche Inc., Nutley, land, PP-

N.J. Primary Examiner-J0seph M. Golian [22] Flled' 1973 Attorney, Agent, or Firm-Samuel L. Welt; Jon S. [21] Appl. No.: 350,662 Saxe; William H. Epstein Related U.S. Application Data [62] Division of Ser. No. 4,134, Jan. 19, 1970, Pat. No. [57] ABSTRACT 3,760,087. The present invention comprises perfume and flavored compositionsvcontaining ethyl 2,4-di0x0hexan0ate. [52] U.S. Cl. 426/65 51 Im. Cl A23! 1/26 3 Clams Drawmgs PERFUME AND F LAVOREI) COMPOSITIONS CONTAINING ETHYL 2,4-DIOXOHEXANOATE This is a division, of application Ser. No. 4,134, filed Jan. 19, 1970, originally entitled PERFUME AND FLAVORED COMPOSITIONS CONTAINING ETHYL 2,4-DIOXOl-IEXANOATE and now US. Pat. No. 3,760,087.

This invention relates to ethyl 2,4-dioxohexanoate as a component of perfume and flavored compositions i.e., as an olfactory and flavoring ingredient.

In particular, the present invention comprises the discovery that ethyl 2,4-dioxohexanoate has a high odor value and desirable blending properties so as to be useful in perfume compositions. This invention also includes the discovery that ethyl 2,4-dioxohexanoate has a flavor value for use in flavored compositions.

The application of odiferous principles to commercial compositions like soaps, cosmetics, creams, powders, and lotions involves a multitude of complex problems. For example, soaps having unpleasant and sometimes offensive odors cannot be successfully marketed without counteracting such undesirable characteristics. The magnitude of this problem is especially great since soaps are an inexpensive commodity and cannot justify the use of precious odorants. Accordingly, a major consideration in the selection of an olfactory ingredient is its economical coverage over the products objectionable character.

To be useful as an olfactory ingredient, a compound must be fragrant and as pleasant as possible, yet not interfere with the purpose for which the final product is intended by significantly affecting factors like solubil-' ity, toxicity, color, etc. For example, soap incorporating an olfactory ingredient should desirably result in a finished product having a uniform fragrance, high odor stability and effective coverage for the unpleasant odor.

Although many fragrant compounds impart desirable odors, their use may be precluded by the fact that they are either too costly and/or interfere with the purpose for which they were intended. For this reason, many fragrant compounds are not suitable to use in compositions such as soaps, bath salts, shampoos, cosmetics, creams, lotions, etc. Ethyl 2,4-dioxohexanoate is acceptable for use in such compositions, especially since the use of the compound produces economical odor coverage.

The perfume compositions comprising the present invention provide pleasing odors which can be characterized as burnt caramel, opopanax, Cassia absolute, Genet absolute, Tuberose absolute and butterscotch.

As a compound reminiscent of such odors, ethyl 2,4- dioxohexanoate is valuable for use in perfumery, especially since the compound can also be blended with other fragrances to obtain perfume compositions which have widely varying odor characteristics. For example an olfactory effective amount of ethyl 2,4- dioxohexanoate can be incorporated into any of several perfume bases to produce perfume compositions such as cosmetics, soaps, lotions, aerosols, creams, powders and the like. As used herein, the term perfume bases comprehends materials into which the fragrant ethyl 2,4-dioxohexanoate compound is added; and the term olfactory effective amount" denotes that amount of ethyl 2,4-dioxohexanoate which is added to a perfume base to produce a perfume composition having a pleasing fragrance.

Suitable perfume bases include bubble bath, hair dressing, detergents, bar soaps, lotions, deodorants, sachets, cold creams and the like. Of course, the chemical composition of each perfume base varies. For example, a perfume base such as bubble bath can comprise sodium sesquicarbonate and magnesium carbonate; deodorant dusting powder can comprise tale, hexachlorophene and magnesium carbonate, and after shave lotion can comprise denatured 95% ethyl alcohol, hexachlorophene and diethylene glycol, monoethyl ether. These or any other perfume base can then be converted to a perfume composition by the addition thereto of an olfactory effective amount of ethyl 2,4- dioxohexanoate.

The compound, which is an oily liquid at room temperature, can be incorporated into any of several perfume bases in two basic ways. Firstly, it can be added directly to a perfume base or; secondly, it can be dissolved in an alcoholic or hydro-alcoholic solution. As used herein, the term solution comprehends colognes, extracts, toilet waters, after shave lotions and the like. Desirably the alcohol used in these solutions is denatured 95% ethyl alcohol wherein the denaturant is either (I) diethylpthalate (e.g. for perfume extracts) or (2) brucine sulfate and tert butyl alcohol (e.g. for colognes, toilet waters, etc.). The alcohols used are of two types with a fixative and without a fixative. Fixatives (e.g. pentadecanolide, l5- hydroxypentadecanoice acid lactone) are generally added to perfumery alcohols in order to depress the rawness of the alcohol odor and to hasten the maturing of the olfactory ingredient in solution.

The compound can also be mixed with other olfactory ingredients to produce perfume compositions having a variety of pleasing odors. For example, ethyl 2,4- dioxohexanoate can be mixed with methyl N-3,7- dimethyl-7hydroxyoctyliden-anthranilate, linalyl acetate coeur, linalyl phenal acetate, benzyl acetate, etc. Where mixed with other olfactory ingredients, the resulting compositions can have odors like e.g., Cassia Absolute, Tuberose Absolute and Genet Absolute.

Irrespective of whether the alcohol is fixed, the resulting solution of the olfactory ingredient is aged and then chilled. The solution is desirably aged for at least 24 hours and chilled for about 1-2 hours in the same container which is used for preparing the solution. A solution of deodorant colognes should preferably be aged longer i.e., about 10 days.

The concentration of the olfactory ingredient, namely, ethyl 2,4-dioxohexanoate, varies with the particular kind of solution. For example, a perfume extract can comprise an alcohol and from about l2to about 25% of the olfactory ingredient; and a toilet water can comprise a hydro-alcoholic solution and from about 6 to about 8% of the compound in from about to about alcohol. Similarly, a cologne can comprise up to about 5% of the olfactory ingredient in from about 75 to about 85% alcohol.

All solutions are generally made on a weightzvolume basis except cosmetic solutions (e.g. after shave lotions, deodorant colognes, etc. which are generally made on a weight:weight basis. In the former case the olfactory ingredient is added by weight and the solvent is added on a sufficient quantity (q.s.) basis. Where the solution is hydro-alcoholic, the alcohol is computed as a percentage of the total volume and is added by volume to the established weight of the compound.

Incorporation of the olfactory ingredient into a perfume base is effected by manual stirring. Certain perfume compositions such as talc should, however, be preferably prepared with the aid of a power blender. Regardless of the blending means, sufficient mixing is necessary in order to ensure a thoroughly homogenous distribution of the olfactory ingredient into the perfume base.

Good odorant results are obtained when the olfactory effective amount of ethyl 2,4-dioxohexanoate is up to about 25% of the weight of the perfume composition. Excellent odorant results are obtained when the olfactory effective amount is up to about 5% on the same basis. For example, in bubble bath, the olfactory amount of ethyl 2,4-dioxohexanoate is suitably about 8% by weight. A preferred embodiment utilizes about 5% of the olfactory ingredient.

Where used as a flavoring ingredient, ethyl 2,4- dioxohexanoate is useful for blending with food products to provide compositions having a taste characterized as: apple, butterscotch, butter-nut, maple and maple-honey. Such flavors are of particular advantage in compositions such as confections, jams, jellies, syrups, ice cream and the like. Such compositions can contain, as the flavoring ingredient, ethyl 2,4-dioxohexanoate alone or in an admixture with other flavoring ingredients. For example, the dioxohexanoate compound can be mixed with vanillin, solid extract Foenugreek etc. to produce a syrup which has an imitation maple flavormg.

ln using ethyl 2,4-dioxohexanoate as a synthetic flavoring, an effective amount of the flavoring compound is added to a food carrier to impart a palatable flavor. The relative amount of the flavoring compound in the mixture (flavoring compound food carrier) can be expressed as a percentage of the finished food product. The percentage varies inter alia with the particular kind of food product, taste, etc.

Ethyl 2,4-dioxohexanoate can be incorporated into many food carriers e.g., ice cream, custard, ice milk, water ices, candy, flavor bases, cake mixes, icings, fillings, and the like.

Food palatable results are obtained when the effective amount of the flavoring compound constitutes up to about 5% of the weight of the food product. Excellent palatable results are obtained when the effective amount of the flavoring compound constitutes up to about 1% on the same basis. As noted, the flavoring compound can be used to produce other tasty food products such as table syrup, cream center candy and the like. Where the flavoring compound is utilized in a table syrup, the effective amount of the flavoring compound constitutes from about 0.1 to about 0.5% of the weight of the food product. Likewise, cream center candy and ice cream suitably use from about 0.5% of the weight of the food product. Likewise, cream center candy and ice cream suitably use from about 0.25 to about 1% of the flavoring compound on the same basis.

The olfactory ingredient and flavoring compound, namely, ethyl 2,4-dioxohexanoate, can be prepared by a Claisen condensation of 2-butanone and diethyl oxalate using a solution of sodium ethoxide in ethyl alcohol as the base. Preferably, the ethyl alcohol is anhydrous and has a moisture content of less then 0.15% (by Karl Fischer determination) so as to produce good yields.

Ethyl 2,4-dioxohexanoate has already been described in the literature, for example, in 1906 by Otto Diels in ethyl 2,4-

-69C at 0.4mm/Hg percent 91 98 u II A "0 B.P. Purity (V.P.C. analysis) Empirical formula EXAMPLE 1 Preparation of ethyl 2,4-dioxohexanoate 236 gm of anhydrous ethyl alcohol is distilled directly into a 1,000 ml three-necked flask equipped with a fast agitator, water-cooled condenser, addition funnel, thermometer and gas-inlet/outlet tube. The reaction is conducted under a nitrogen atmosphere. Anhydrous sodium ethoxide (68 gm) is added with agitation and the mixture refluxed for 1 hour. The mixture is then cooled to a range of 0 to 5C whereupon a mixture of 72 gm of 2-butanone and 146 gm of diethyl oxalate is slowly added through the addition funnel over a 30 minute period and under a nitrogen atmosphere at 0 to 5C. The resulting mixture was then further cooled and agitated for 3 hours at 0 to 5C.

After cooling to 0C, 168 ml of a 1:1 hydrochloric acid/ H O (6M) solution was added and the tempera ture of the resultant solution was maintained below 10C. The acidified solution was extracted twice, each time with 300 ml of toluene. The organic phase was then successively washed twice with 600 ml water, once with 600 ml of a 10% Na CO solution and once with 400 ml of a saturated sodium chloride solution. The toluene layers were then separated from the aqueous layers, combined, dried over magnesium sulfate and filtered. The toluene was removed by distillation under 25 mm/Hg pressure yielding ethyl 2,4- dioxohexanoate. Purity (V. P. C.) about 91%. Optional and further purification was effected by fractional distillation through a 6 inch glass Helix packed column at 0.2 mm/Hg. Distillation yielded:

Fract. Vapor Pot. Pressure 1. C 104C 2 0 mm 2. 85C 104C 2.0 mm 3. 86C 112C 2.0 mm 4. 89C 122C 2 0 mm 5. 85C C 2 0 mm Fract. 5 was shown to contain the desired product plus about 56% of unknown by-product. 'Commued lngredients Amount EXAMPL 2 amyl cinnamic aldehyde 280 ml Aurantiol 5720 ml Preparation of Imitation Maple Flavoring 5 balsam mlu Soluble resin 70 ml benzoin siam soluble resin 70 ml An mitatlon maple syrup containing the following benzyl acetate 700 ml ingredients benzyl salicylate 700 ml celery seed oil 70 ml folione 70 ml ethyl 2,4-dioxohexanoate, l0% 500 ml Ingredients 1 m n 10 t indolene, 10% 42 ml iso eugenol extra 154 ml methyl cyclopentenolene g methyl benzoate 350 ml vanillin 50 g methyl salicylate (syn) 364 ml gum balsam peru 5 g methyl tuberate 28 ml alcohol 190 375 ml vanilla soluble odo resin 42 ml solid extract Foenugreek 125 g Ylang bourbon extra 350 ml caramel coloring 185 g 15 elhyl za4dloxohexanoate g Methyl N-3,7-dimethyl-7'hydroxyoctyliden-anthranilate water q. 5.

was prepared (10,000 ml) by:

l. combining the ingredients in the order as above was prepared by: listed, and

1. combining the first seven ingredients above, and adequately mixing each ingredient into the result- 2. bringing the solution up to a final volume of 1,000 ing mix re in order to ensure a homogenous disml with water (q.s.). persion of each ingredienL EXAMPLE 3 EXAMPLE 5 Preparation of Cassia Absolute Perfume Composition Preparation of Genet Absolute Perfume Composition A perfume composition containing the following in- A perfume composition containing the following ingredients and having a Cassia absolute odor gredients and having a Genet absolute odor Ingredients A t Ingredients Amount n-nonyl aldehyde 560 ml benzo pyrone (coumarin) extra l6 ml methyl n-nonyl acetaldehyde 392 ml gr nger crystals ethyl Bnapthyl ll ml anisic aldehyde 280 ml ketone anisyl aldehyde 280 ml lauryl acetate l ml benzyl alcohol (P.G.)* 2240 ml n'nonyl ld yd 1 in l 1 ml citronellol extra 168 ml dlpropylene glycol cuminic aldehyde 56 ml n-decyl aldehyde 1 1 ml dipropylene glycol l48 ml n-d ecyl a ol 3 ml methyl 2-octynoate 560ml AnlSlC A hyde 5 ml geraniol 560 ml Aurantiol 50 3 ml geranyl butyrate 392 ml 40 Benzyl Alcohol P.G.* 415 ml ethyl 2,4-dioxohexanoate 10% 500 ml l f t 5 29 ml benzopyrrolefindol) 10% in aldehyde. 10% 5 ml triethanolamine 280 ml dlpropylene glycol z l pure 1% 112 ml ethyl phenyl acetate 5 ml beta-ionone 560 ml ethyl propronate 5 ml hydroxycitronellal ll20 ml follone 1% In dipropylene glyc 5 ml linalool coeur 280 ml geraniol 3 ml methyl salicylate(syn) 560 ml ethyl 2,4-dioxohexanoate 10 ml p-methyl acetophenone, 10% H2 ml ndol 10 ml styrax soluble resin 560 ml 150 geno 52 ml terpineol extra 280 ml Labdanum soluble resin 52 ml laurine extra 52 ml linalyl acetate coeur 6 ml perfume grade llnalyl phenyl acetate 52 ml methyl aceto phenone 10 ml was prepared (10,000 ml) by: Peru balsam soluble resin I24 ml phenyl ethyl alcohol extra 2| ml 1. COIIlblllll'lg the ingredients in the order as above when (EU 83 ml listed, and 2. adequately mixing each ingredient into the result- Perfume grade ing mixture in order to ensure a homogenous dis- 55 persion of each ingredient. was p p f f 9 y l. combining the ingredients in the order as above EXAMPLE 4 listed, and preparation f T b Ab l Pe f me 2. adequately mixing each ingredient into the result- Composition ing mixture in order to ensure a homogenous disrs' h 'n edie t. A perfume composition containing thefollowlng [11- pe Ion of eac 1 gr n gredients and having a Tuberose absolute odor EXAMPLE 6 Preparation of Scented Bar Soap lngredlenls Amoum A scented bar soap composition IS produced by mmethyl n-nonyl acetaldehyde 7 ml corporating the perfume composition prepared in Exgamma-nonalactone 420 ml ample 5 into soap chips in the following manner so that the finished product contains about 1% by weight, of

EXAMPLE 7 Preparation of Scented Bath Salts A scented bath salts composition is produced by incorporating ethyl 2,4-dioxohexanoate into the following ingredients in the following manner so that the finished composition contains about by weight, of the dioxohexanoate compound:

Ingredients Amount sodium sesquicarbonate 90 magnesium carbonate 5 ethyl 2,4-dioxohexanoate 5 was prepared by:

l. grinding the ethyl 2,4-dioxohexanoate into the magnesium carbonate in a milling apparatus,

2. adding the perfumed magnesium carbonate to the sodium sesquicarbonate in a powder mixing apparatus, and

3. mixing the resulting mixture until the powders are thoroughly dispersed.

We claim:

1. A flavored composition comprising an effective amount of ethyl 2,4-dioxohexanoate as a flavoring ingredient in a food.

2. The flavored composition of claim 1 wherein the effective amount of ethyl 2,4-dioxohexanoate is present in an amount of up to 5% of the weight of said flavored composition.

3. The flavored composition of claim 1 wherein the effective amount of ethyl 2,4-dioxohexanoate is present in an amount of up to 1% of the weight of said flavored composition. 

2. The flavored composition of claim 1 wherein the effective amount of ethyl 2,4-dioxohexanoate is present in an amount of up to 5% of the weight of said flavored composition.
 3. The flavored composition of claim 1 wherein the effective amount of ethyl 2,4-dioxohexanoate is present in an amount of up to 1% of the weight of said flavored composition. 